Synthesis, Characterization and Properties of Some Main-Chain Ferrocene-Based Polymers Containing Aromatic Units

Four main-chain ferrocene-based polymers containing aromatic units, including poly(o-Cresolphthalein 1,1′-ferrocene dicarboxylate) (PCPFD), poly(cresol red 1,1′-ferrocene dicarboxylate) (PCRFD), poly(2,4-quinolinediol 1,1′-ferrocene dicarboxylate) (PQDFD), and poly(sudan orange G 1,1′-ferrocene dicarboxylate) (PSOFD), were successfully synthesized. The solution polycondensation reaction was employed for the synthesis of PCPFD and PCRFD while PQDFD and PSOFD were synthesized via an interfacial polycondensation reaction. The synthesized polymers were characterized by ¹H and ¹³C NMR, UV–VIS absorption and FTIR spectra and X-ray diffraction. The synthesized main-chain ferrocene-based polymers are generally amorphous. The effect of organic solvent, scan rate, electrolyte concentration and [Fe] concentration on the cyclic voltammetric behavior of the synthesized polymers were examined. The thermal properties were investigated employing thermogravimetric analysis. The results revealed the relative thermal stability of the polymers. The liquid crystalline properties were studied. The results indicated that the synthesized polymers exhibited nematic phases during the scan cycles of heating and cooling with high phase duration.     

Arylidene polymers. XVIII. Synthesis and thermal behavior of organometallic arylidene polyesters containing ferrocene derivatives in the main chain

A new interesting category of organometallic polyesters based on diarylidenecycloalkanones containing ferrocene derivatives in the polymer main chain has been prepared by interfacial polycondensation of 1,1′-dichlorocarbonyl ferrocene or 1,1′-dichlorocarbonyl-4,4′-diiodoferrocene with 2,5-bis(p-hydroxybenzylidene)cyclopentanone, 2,5-divanillylidenecyclopentanone, 2,6-bis(p-hydroxybenzylidene)cyclohexanone, 2,6-divanillylidenecyclohexanone, and 2,7-bis(p-hydroxybenzylidene) cycloheptanone. The resulting polyesters were characterized by elemental analyses, infrared spectroscopy, solubility, and viscometry measurements. The thermal behavior of the synthesized polymers was evaluated by thermal gravimetric analysis and correlated with their structures. The crystallinity of all polymers were examined by x-ray diffraction analysis. Moreover, the electrical conductivity of a selected example of polymer was investigated above the temperature range (300–500 K) and showed that it followed an Arrhenius-type equation with activation energy 2.09 eV. © 1993 John Wiley & Sons, Inc.     

含二茂铁基的酰肼化合物的合成

以二茂铁二甲酰氯和芳甲酰肼为原料,采用微波法合成了9个N2,N2'-二芳甲酰基-1,1'-二茂铁二甲酰肼类化合物Ⅲ,并通过IR、1HNMR和ESI/MS对其结构进行了表征。紫外光谱研究表明,含吸电子取代基的化合物Ⅲf对阴离子F-、CH3COO-有识别作用,化合物Ⅲh、Ⅲi对F-、CH3COO-、H2PO4-有识别作用。初步的生物活性测试表明,取代基位于邻位的化合物Ⅲa、Ⅲb和Ⅲc对金黄色葡萄球菌、大肠杆菌有良好的抑菌作用。     

Synthesis and Properties of a Ferrocene-based Metallomesogenic Polymer Containing Bis(4-hydroxyoctoxyphenyl)sulfone

Poly[bis(4-hydroxyoctoxyphenyl)sulfone 1,1′-ferrocene dicarboxylate] (PHOSFD) was synthesized by solution polycondensation reaction of bis(4-hydroxyoctoxyphenyl)sulfone with 1,1′-ferrocenyl chloride. The synthesized polymer was characterized via the measurement of its ¹H NMR spectrum, UV–Vis spectrum and FTIR spectrum. X-ray diffraction pattern was measured to investigate the crystallinity of the synthesized polymer and it was found that the polymer is mostly amorphous. The molecular weight of the polymer was determined by gel permeation chromatography. In addition, the electrochemical, the thermal, and the liquid crystalline properties of the synthesized polymer were examined and compared with the properties of poly(diethyleneglycol 1,1′-ferrocene dicarboxylate) (PDEFD) that was synthesized in our earlier study. The electrochemical processes of PHOSFD in CH₂Cl₂ were confirmed neither to be totally reversible nor completely irreversible. Generally, the electrochemical properties of PHOSFD and PDEFD were found to be similar to each other. PHOSFD was found to be thermally stable but its thermal stability is lower than that of PDEFD. Both of PHOSFD and PDEFD showed liquid crystalline properties and they possessed nematic phase textures with schlieren disclinations during heating and cooling.     

二茂铁甲酸封端不饱和聚酯的固化及热性能研究

以乙二醇、反丁烯二酸为原料合成的不饱和聚酯作为主链,二茂铁甲酸(FCA)作为封端剂,合成了含二茂铁基的不饱和聚酯(RFc),采用红外光谱对产物结构进行了表征。采用DSC及TGA研究了不同二茂铁甲酸含量对不饱和聚酯树脂固化性能和热稳定性的影响。结果表明,随着二茂铁甲酸含量的增加,RFc树脂固化反应活性减弱,热稳定性下降。其最高放热峰温度在171～173℃,且具有比较宽的加工温度范围(152～195℃),符合模塑料固化工艺要求。树脂的耐热性较好,初始热分解温度约为340℃,N2气氛下600℃残炭率可达19.76%。     

苯甲酸封端间苯型不饱和聚酯树脂的合成及性能研究

本文合成了苯甲酸封端的间苯型不饱和聚酯树脂,并就树脂中苯乙烯的含量、浇铸体的后固化时间对树脂性能的影响和浇铸体的耐酸、耐碱性能进行了研究。研究结果表明,苯乙烯的含量在35~40%之间,后固化时间为10h,树脂的性能达到最佳;苯甲酸封端后的间苯型不饱和聚酯树脂的耐酸、耐碱性能均有所提高。     

Structure and properties of p-carboxysuccinanilic polyester resins

Polyester resins were prepared by the reaction of p-carboxysuccinanilic acid ethyl ester with ethylene glycol and 1,4-butenediol. Also, unsaturated polyester resins were prepared by the copolymerization of p-carboxysuccinanilic acid ethyl ester and maleic anhydride with ethylene glycol, 1,6-hexanediol, 1,4-butenediol, and 2-butyne-1,4-diol. All the polyester resins and the copolyesters have been characterized and were found to cure with styrene, except those prepared in the absence of maleic anhydride. The properties of the cured products in the form of films were determined. Infrared and nuclear magnetic resonance (NMR) spectroscopy were used for both qualitative and quantitative analyses of the polyester resins and their hydrolyzate products after curing with styrene.     

Methacrylate monomer as an alternative to styrene in typical polyester–styrene copolymers

This study presents the research on the influence of crosslinking monomers [styrene and diethylene glycol dimethacrylate (DEGDMA)] on the properties of unsaturated polyester resins (UPRs). Syntheses of the unsaturated polyesters (UPs) modified with benzyl alcohol were carried out. Then, each polyester was used in preparation of five resin solutions with different amounts of crosslinking monomers acting as reactive diluents. These diluents improve the processability of UPs reducing their viscosities. They also take part in crosslinking of resins during copolymerization process. The properties of the prepared UPRs systems were investigated before and after the curing process. The measurements of their viscosity, reactivity, mechanical properties, thermal stability (thermogravimetry), and dynamic mechanical analysis were performed. Resins where DEGDMA was used as reactive diluent were characterized by the largest viscosities in comparison to styrene ones. The type of the used monomer influenced also degree of the resin crosslinking. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47735.     

水溶性苯乙烯改性醇酸树脂的合成工艺研究

采用脂肪酸法合成基础醇酸树脂,然后用苯乙烯和丙烯酸接枝共聚,制得了水溶性苯乙烯改性醇酸树脂.通过探讨油度、K值、苯乙烯、丙烯酸用量等因素对改性后树脂成膜性能的影响,确定了水溶性苯乙烯改性醇酸树脂的最佳工艺和配方;同时比较了水溶性常规未改性醇酸清漆、溶剂型苯乙烯改性醇酸清漆与水溶性苯乙烯改性醇酸清漆的性能优劣.结果表明:水溶性苯乙烯改性醇酸树脂较未改性醇酸树脂干性、硬度有了较大提高,与溶剂型苯乙烯改性醇酸树脂相当;当选取油度60％、K值1.05、苯乙烯质量分数35％、丙烯酸质量分数6.5％时,水溶性苯乙烯改性醇酸树脂白干表干达到0.5 h,实干20 h,硬度HB,水溶性优异,漆膜耐水、耐碱性获得很大提高,同时兼具了性能要求和环保要求.     

Fatty acid-based monomers as styrene replacements for liquid molding resins

One method of reducing styrene emissions from vinyl ester (VE) and unsaturated polyester resins (UPE) is to replace some or all of the styrene with fatty acid-based monomers. Methacrylated fatty acid (MFA) monomers are ideal candidates because they are inexpensive, have low volatilities, and free-radically polymerize with vinyl ester. The viscosity of VE resins using these fatty acid monomers ranged from 700-2000 cP, which is considerably higher than that of VE/styrene resins (∼100 cP). In addition, the T_g of VE/MFA polymers were only on the order of 80 °C, which is significantly lower than that of VE/styrene polymers. Decreasing the length of the base fatty acid chains from 18 to 12 carbon atoms improved the T_g by 20 °C, while lowing the resin viscosity from ∼2500 to ∼1000 cP. Residual unsaturation sites on the fatty acid backbone decreased the cure rate of the resins thereby decreasing polymer properties. Ternary blends of VE, styrene, and fatty acid monomers also effectively improved the flexural, fracture, and thermo-mechanical properties and reduced the resin viscosity to acceptable levels, while using less than 15 wt% styrene, far less than commercial VE resins.     

Block copolymers of unsaturated polyesters and functional elastomers

Block copolymers of unsaturated polyester were prepared by condensation polymerization of hydroxyl or carboxyl terminated liquid rubbers with maleic anhydride, phthalic anhydride, and propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. In this study, copolymers of unsaturated polyesters with hydroxy terminated polybutadiene, carboxy terminated nitrile rubber, and hydroxy terminated natural rubber were prepared. Mechanical properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after the resin was cured in appropriate molds for comparison with the control resin. The fracture toughness and impact resistance of CTBN‐modified unsaturated polyester show substantial improvement by this copolymerization without seriously affecting any other property. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1956–1964, 2004     

Curable resins based on recycled poly(ethylene terephthalate) for coating applications

Poly(ethylene terephthalate) waste was depolymerised in the presence of diethylene- or tetraethylene glycol and manganese acetate as a catalyst. An epoxy resin was then prepared by the reaction of these oligomers with epichlorohydrin in presence of NaOH as a catalyst. The produced oligomers were condensed with maleic anhydride and ethylene glycol to produce unsaturated polyester. The chemical structures of the resulting epoxy and unsaturated polyester resins were confirmed by ¹HNMR. The vinyl ester resins were used as cross-linking agents for unsaturated polyester resin diluted with styrene, using free radical initiator and accelerator. The 2-amino ethyl piprazine was used as hardener for epoxy resins. The curing behaviour of the unsaturated polyester resin, vinyl ester resins and styrene was evaluated at different temperatures ranged from 25 to 55 °C to calculate the curing activation energy of the system. The cured epoxy and unsaturated polyester resins were evaluated in coating application of steel.     

Compressive Properties and Curing Behaviour of Unsaturated Polyester Resins in the Presence of Vinyl Ester Resins Derived from Recycled Poly(ethylene terephthalate)

Poly(ethylene terephthalate) waste was depolymerised in the presence of tetraethylene glycol and manganese acetate as a catalyst, so as to produce oligomers. An epoxy resin was then prepared by the reaction of these oligomers with epichlorohydrin in presence of NaOH as a catalyst. New diacrylate and dimethacrylate vinylester resins were then synthesized by reaction of the terminal epoxy groups with acrylic and methacrylic acid in the presence of triphenyl phosphite as a catalyst. The chemical structures of the resulting vinyl ester resins were confirmed by ¹HNMR. The vinyl ester resins were used as crosslinking agents for unsaturated polyester resin diluted with styrene, using free radical initiator and accelerator. The curing behaviour of the unsaturated polyester resin, vinyl ester resins and styrene was evaluated at temperatures from 25 to 55 ^○C. The compression properties of the cured resins, having different vinyl ester contents and different cure temperatures, were evaluated. Increasing the cure temperature and the vinyl ester content led to a pronounced improvement in the compression strength and Young’s modulus.     

Studies on sand/clay unsaturated polyester composite materials

The effect of a radiation‐initiated polyester on the physicomechanical properties of a sand/clay‐polyester composite has been investigated. The unsaturated polyester resins containing various styrene contents were used at different sand/clay composites from 10 to 70 wt % with respect to the weight of sand and clay together; polymerization was conducted using γ‐irradiation at 50 kGy. Also, different particle sizes of clay (namely 1.25–0.80, 0.80–0.50, and <0.50) were used. The compressive strength, apparent porosity, and water absorption—in addition to infrared spectroscopy of the composite samples—were studied. Results indicate that the compressive strength decreases with an increase in sand/clay, as well as the styrene content in the unsaturated polyester resin, whereas the apparent porosity and water absorption of the composite samples increase. Infrared spectra showed the appearance of new bands, which indicated a chemical reaction between polyester and clay constituents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1031–1038, 1999     

Unsaturated polyester resins based on rosin maleic anhydride adduct as corrosion protections of steel

Unsaturated polyester resin (UP), based on 1 mol maleopimaric adduct (MPA), 1 mol maleic anhydride, 1 mol isophthalic acid, 1 mol adipic acid, 1 mol propylene glycol, and 1 mol diethylene glycol, were obtained at various times during polyesterification. They were characterized by ¹H NMR and chemical titration. Increasing the reaction time to 8 h led to an increase in (a) the number-average molar mass (Mn), (b) the glass transition temperature (T_g) and (c) the compatibility with styrene. Several of these fractions were cured with styrene, in amount of UP/ST = 2.5 (weight of styrene, ST, and unsaturated polyester, UP), using initiator and activator. The curing behaviors of cured UP resins with styrene were evaluated by DSC measurements. The prepared UP curable resins were evaluated in the field of steel coating by measuring their mechanical properties and chemical resistance. The corrosion resistance of cured films was evaluated using salt fog resistance test.     

基于二聚脂肪酸改性苯乙烯聚酯树脂的合成及性能

以C₃₆二聚脂肪酸、邻苯二甲酸酐、顺丁烯二酸酐和1,2-丙二醇为原料合成不饱和聚酯树脂（UPR）。以苯乙烯为交联剂、过氧化苯甲酰为引发剂,固化后得到C₃₆二聚脂肪酸（DFA）改性苯乙烯聚酯树脂。采用FT-IR和SEM表征树脂结构及拉伸断面形貌,研究发现DFA引入树脂主链且发生反应,树脂断裂方式由脆性断裂转变为韧性断裂。通过TG、DSC、拉伸、弯曲、硬度和耐溶剂实验研究了DFA用量对树脂热稳定性、力学性能和耐溶剂性能的影响。当DFA含量为6%（摩尔分数）时,改性UPR材料的综合性能最佳,初始热分解温度由147℃增加到201℃,玻璃化转变温度由146.6℃降低到120.7℃,拉伸强度、断裂伸长率、弹性模量、邵氏硬度、弯曲强度分别是未改性树脂的7.23、2.90、7.84、1.63、5.12倍,而且耐溶剂损失率均降低70%以上。DFA可以改善苯乙烯聚酯树脂的柔韧性,是一种有效的增韧改性剂。     

Preparation of Triazole-furnished Ferrocene Derivatives and their Polymer Complexes of Silver(I)

Condensation reactions of feroccenemethanol and of 1,1′-feroccenedimethanol with benzotriazole and triazole produce the ferrocene derivatives with one or two N-azole-containing substituents bonded to the cyclopentadienyl ligands. The bifunctional ferrocene derivatives, 1,1′-bis[(1,2,3-benzotriazol-1-yl)methyl]ferrocene and 1,1′-bis(1,2,4-triazoyl)ferrocene, reacts with [Ag(MeCN)₄]PF₆ to cause separation of the macromolecular complexes from the solution. The former ferrocene derivative with benzotriazole groups yields the complex of Ag(I) with Ag:ligand = 2:3. The Ag center is bonded to three triazole groups, forming a trigonal structure. Crystals of the complexes contain the ladder-shaped sheets formed by Ag(I) and the ligand, and these sheets are aligned in a staggered fashion. The latter ligand with 1,2,4-triazole groups and Ag(I) yield the 1:1 complex. Counter anions and MeCN molecules are contained within holes formed by the Ag(I) centers bonded with a metal–metal bond and the bifunctional ligands. NMR and UV measurement of the MeCN solution of these macromolecular complexes revealed dissociation of the ligand and degradation of the complexes in solution. This paper is dedicated to Professor Takakazu Yamamoto in honor of his pioneering research efforts and accomplishments in the fields of organometallics and π-conjugated polymers.     

Preparation and structural characterisation of a novel ferrocene–amino acid conjugate

A new type of ferrocene–amino acid conjugate, 2-[(methoxycarbonyl)methyl]-2-aza[3]ferrocenophane (1), was obtained in a rather low yield via condensation reaction of 1,1′-bis(hydroxymethyl)ferrocene and glycine methyl ester in the presence of [RuCl₂(PPh₃)₃] as a catalyst. The compound was characterised by combustion analysis and by spectroscopic method, and its solid-state structure was established by single-crystal X-ray diffraction analysis. Compound 1 is reluctant towards alkylation with MeI but readily forms a stable picrate salt. Cyclic voltammetry experiments on 1 (in CH₃CN at Pt electrode) revealed the compound to undergo a one-electron reversible oxidation attributable to ferrocene/ferrocenium couple (E^o′ = ?5 mV vs. ferrocene itself), which shifts towards more positive potentials upon protonation with HCl.     

回收溶剂对EPDM/St-An接枝反应行为及AES性能的影响

以甲苯/正庚烷为溶剂,用溶液聚合法合成三元乙丙橡胶(EPDM)-苯乙烯(St)-丙烯腈(An)接枝共聚物(EPDM-g-SAN),用常压蒸馏法回收并提纯溶剂。以回收溶剂与新溶剂按比例混合,用于EPDM-g-SAN的合成。研究了EPDM/St-An的接枝共聚合反应行为以及EPDM-g-SAN与SAN树脂共混制备的AES。用气相色谱质谱分析了回收溶剂的组成,用FTIR及TG分析了回收溶剂的用量分别对接枝产物的结构和AES的热稳定性的影响。结果表明,回收溶剂有乙苯生成,并存在残留单体;回收溶剂中的甲苯、丙烯腈、甲基环己烷和3-甲基己烷的相对含量随回收次数的增加而提高,正庚烷和苯乙烯含量则有减少趋势;回收溶剂的用量对接枝共聚合反应行为和接枝产物的结构,以及对AES的冲击强度、拉伸性能、弯曲性能、熔体流动速率和热稳定性的影响甚微。     

A double-stranded 1D-coordination polymer assembled using the tetravergent ligand 1,1′-bis(4,2′:6′,4″-terpyridin-4′-yl)ferrocene

1,1′-Bis(4,2′:6′,4″-terpyridin-4′-yl)ferrocene (1) reacts with ZnCl₂ to yield a double-stranded 1D-coordination polymer [{Zn₂(1)Cl₄}∙3CHCl₃]_n. The 1,1′-functionalized ferrocene core adopts a cisoid-conformation, giving rise to a folded conformation for 1 and a double-stranded 1D-polymer chain. This contrasts with previously reported multi-stranded chains supported by 4,2′:6′,4″-terpyridine ligands in which the multiple-nature of the chain arises from multinuclear metal nodes.